microbiocidal phenylamidine derivatives

专利摘要:
Compounds of formula (I) (I)wherein the substituents are as defined in claim 1.Furthermore, the present invention relates to agrochemical compositions comprising compounds of the formula (I), to the preparation of these compositions and to the use of the compounds or compositions in agriculture or horticulture to combat, prevent or control plant infestation, collected food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.
公开号:BR112020011083A2
申请号:R112020011083-3
申请日:2018-11-29
公开日:2020-11-17
发明作者:Sarah Sulzer-Mosse；Benjamin PINSON
申请人:Syngenta Participations Ag；
IPC主号:

专利说明:

[001] [001] The present invention relates to microbiocidal phenylamidine derivatives, e.g., as active ingredients, which have microbiocidal activity, in particular fungicidal activity. The invention also relates to the preparation of these phenylamidine derivatives, with intermediates useful in the preparation of these phenylamidine derivatives, with the preparation of these intermediates, with agrochemical compositions comprising at least one of the phenylamidine derivatives, with the preparation of these compositions and with the use of phenylamidine derivatives or compositions in agriculture or horticulture to control or prevent infestation of plants, collected food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.
[002] [002] Certain fungicidal phenylamidine compounds are described in WO 2000/046184.
[003] [003] It has now surprisingly been discovered that certain new phenylamidine derivatives have favorable fungicidal properties.
[004] [004] The present invention therefore provides compounds of formula (I) n (I) in which
[005] [005] In a second aspect, the present invention provides an agrochemical composition comprising a compound of formula (I).
[006] [006] The compounds of formula (I) can be used to control phytopathogenic microorganisms. Thus, in order to control a phytopathogen, a compound of formula (I), or a composition comprising a compound of formula (I), according to the invention can be applied directly to the phytopathogen, or to the locus of a phytopathogen, in particular to a plant susceptible to attack by phytopathogens.
[007] [007] Thus, in a third aspect, the present invention provides the use of a compound of the formula (I), or a composition comprising a compound of the formula (I), as described herein to control a phytopathogen.
[008] [008] In an additional aspect, the present invention provides a method of controlling phytopathogens,
[009] [009] The compounds of formula (I) are particularly effective in controlling phytopathogenic fungi.
[010] [010] Thus, in a still further aspect, the present invention provides the use of a compound of the formula (I), or a composition comprising a compound of the formula (I), as described herein to control phytopathogenic fungi.
[011] [011] In a further aspect, the present invention provides a method of controlling phytopathogenic fungi, comprising applying a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to said fungi phytopathogenic, or to the locus of the aforementioned phytopathogenic fungi, in particular to a plant susceptible to attack by phytopathogenic fungi.
[012] [012] Where the substituents are indicated as being optionally substituted, this means that they may or may not carry one or more identical or different substituents, eg, one to four substituents. Typically, no more than three of such optional substituents are present at the same time. Preferably, no more than two such optional substituents are present at the same time (i.e., the group can be optionally substituted by one or two of the substituents indicated as "optional"). Where the "optional substituent" group is a larger group, such as cycloalkyl or phenyl, it is most preferred that only such an optional substituent is present. Where a group is indicated as being substituted, e.g., alkyl, this includes those groups that are part of other groups, e.g., alkyl on alkylthio.
[013] [013] The term "halogen" refers to fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
[014] [014] Alkyl substituents (either alone or as part of a larger group, such as alkoxy-, alkylthio-) can be straight or branched. Alkyl alone or as part of another substituent is, depending on the number of carbon atoms mentioned, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and their isomers, for example example, iso-propyl, iso-butyl, sec-butyl, tert-butyl or iso-amyl.
[015] [015] Cycloalkyl substituents can be saturated or partially unsaturated, preferably fully saturated and are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
[016] [016] Haloalkyl groups (either alone or as part of a larger group, eg haloalkyloxy) may contain one or more identical or different halogen atoms and, for example, may represent CH2Cl, CHCl2, CCl3, CH2F, CHF2 , CF3, CF3CH2, CH3CF2, CF3CF2 or CCl3CCl2.
[017] [017] Aloxy means a radical -OR, where R is alkyl, e.g., as defined above. Alkoxy groups include, but are not limited to, methoxy, ethoxy, 1-methylethyloxy, propoxy, butoxy, 1-methylpropoxy and 2-methylpropoxy.
[018] [018] The presence of one or more possible asymmetric carbon atoms in a compound of formula (I) means that the compounds can occur in optically isomeric forms, i.e., enantiomeric or diastereoisomeric forms. Atropisomers can also occur as a result of restricted rotation around a single bond. Formula (I) is intended to include all of these possible isomeric forms and mixtures thereof. The present invention includes all of these possible isomeric forms and mixtures thereof for a compound of formula (I). Likewise, formula (I) is intended to include all possible tautomers. The present invention includes all possible tautomeric forms for a compound of formula (I).
[019] [019] In each case, the compounds of the formula (I) according to the invention are in free form, in the oxidized form as an N-oxide or in the form of salt, e.g., an agronomically usable salt form.
[020] [020] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described for example in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
[021] [021] Preferred values for R1, R2, R3, R4, R5, X and n are, in any combination, as shown below: Preferably, R1 and R2 are each independently C1-C4 alkyl.
[022] [022] More preferably, R1 and R2 are each independently selected from methyl, ethyl and isopropyl.
[023] [023] Even more preferably, R1 is methyl, ethyl or isopropyl and R2 is methyl or ethyl.
[024] [024] Most preferably, R1 is ethyl or isopropyl and R2 is methyl.
[025] [025] Preferably, R3 is halogen or C1-C3 alkyl.
[026] [026] More preferably, R3 is fluorine, chlorine or methyl.
[027] [027] Even more preferably, R3 is chlorine or methyl.
[028] [028] Most preferably, R3 is methyl.
[029] [029] Preferably, R4 and R5 are each independently selected from hydrogen and methyl, or R4 and R5 together with the carbon atom to which they are attached form a carbonyl group.
[030] [030] More preferably, R4 and R5 are both hydrogen, or R4 and R5 together with the carbon atom to which they are attached form a carbonyl group.
[031] [031] Most preferably, R4 and R5 are both hydrogen.
[032] [032] Preferably, X is O or S.
[033] [033] Most preferably, X is O.
[034] [034] Most preferably, n is 1.
[035] [035] Modalities according to the invention are provided as shown below.
[036] [036] Mode 1 provides compounds of the formula (I), or a salt, stereoisomer or N-oxide thereof, as defined above.
[037] [037] Mode 2 provides compounds according to mode 1, or a salt thereof, stereoisomer or N-oxide, wherein R1 and R2 are each independently C1-C4 alkyl.
[038] [038] Mode 3 provides compounds according to mode 1 or 2, or a salt thereof, stereoisomer or N-oxide, where R3 is halogen or C1-C3 alkyl.
[039] [039] Mode 4 provides compounds according to any one of modalities 1, 2 or 3, or a salt thereof, stereoisomer or N-oxide, where R4 and R5 are each independently selected from hydrogen and methyl, or R4 and R5 together with the carbon atom to which they are attached form a carbonyl group.
[040] [040] Mode 5 provides compounds according to any one of modalities 1, 2, 3 or 4, or a salt, stereoisomer or N-oxide thereof, where X is O or S.
[041] [041] Mode 6 provides compounds according to any one of modalities 1, 2, 3, 4 or 5, or a salt, stereoisomer or N-oxide thereof, wherein R1 and R2 are each independently selected from methyl, ethyl and isopropyl.
[042] [042] Mode 7 provides compounds according to any one of modalities 1, 2, 3, 4, 5 or 6, or a salt, stereoisomer or N-oxide thereof, wherein R3 is fluorine, chlorine or methyl.
[043] [043] Mode 8 provides compounds according to any one of modalities 1, 2, 3, 4, 5, 6 or 7, or a salt thereof, stereoisomer or N-oxide, where R4 and R5 are both hydrogen, or R4 and R5 together with the carbon atom to which they are attached form a carbonyl group.
[044] [044] Mode 9 provides compounds according to any one of modalities 1, 2, 3, 4, 5, 6, 7 or 8, or a salt, stereoisomer or N-oxide thereof, where R1 is methyl, ethyl or isopropyl and R2 is methyl or ethyl.
[045] [045] Mode 10 provides compounds according to any one of modalities 1, 2, 3, 4, 5, 6, 7, 8 or 9, or a salt, stereoisomer or N-oxide thereof, wherein R3 is chlorine or methyl.
[046] [046] Mode 11 provides compounds according to any of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, or a salt, stereoisomer or N-oxide thereof, where R1 is ethyl or isopropyl and R2 is methyl.
[047] [047] Mode 12 provides compounds according to any one of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, or a salt, stereoisomer or N-oxide thereof, wherein R3 is methyl.
[048] [048] Mode 13 provides compounds according to any one of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, or a salt, stereoisomer or N-oxide thereof, where R4 and R5 are both hydrogen.
[049] [049] Mode 14 provides compounds according to any of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, or a salt, stereoisomer or N- oxide, where n is 1.
[050] [050] Mode 15 provides compounds according to any of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, or a salt, stereoisomer or N-oxide, where X is O.
[051] [051] A preferred group of compounds according to the invention are those of formula (I-1) which are compounds of formula (I) in which R1 and R2 are each independently C1-C4 alkyl; R3 is halogen or C1-C3 alkyl; R4 and R5 are each independently selected from hydrogen and methyl, or R4 and R5 together with the carbon atom to which they are attached form a carbonyl group; X is O, S or NCH3; n is 0 or 1; or a salt, stereoisomer or N-oxide thereof.
[052] [052] A group of compounds according to this modality are compounds of the formula (I-1a) which are compounds of the formula (I-1) where X is O.
[053] [053] Another group of compounds according to this modality are compounds of the formula (I-1b) which are compounds of the formula (I-1) where X is S.
[054] [054] Another group of compounds according to this modality are compounds of the formula (I-1c) which are compounds of the formula (I-1) where X is NCH3.
[055] [055] An additional preferred group of compounds according to the invention are those of formula (I-2) which are compounds of formula (I) in which R1 and R2 are each independently selected from methyl, ethyl and isopropyl; R3 is fluorine, chlorine or methyl; R4 and R5 are both hydrogen, or R4 and R5 together with the carbon atom to which they are attached form a carbonyl group; X is O, S or NCH3; n is 0 or 1; or a salt, stereoisomer or N-oxide thereof.
[056] [056] A group of compounds according to this modality are compounds of the formula (I-2a) which are compounds of the formula (I-2) where X is O.
[057] [057] Another group of compounds according to this modality are compounds of the formula (I-2b) which are compounds of the formula (I-2) where X is S.
[058] [058] Another group of compounds according to this modality are compounds of the formula (I-2c) which are compounds of the formula (I-2) in which X is NCH3.
[059] [059] An additional preferred group of compounds according to the invention are those of formula (I-3) which are compounds of formula (I) in which R1 is methyl, ethyl or isopropyl and R2 is methyl or ethyl; R3 is chlorine or methyl; R4 and R5 are both hydrogen, or R4 and R5 together with the carbon atom to which they are attached form a carbonyl group; X is O, S or NCH3; n is 0 or 1; or a salt, stereoisomer or N-oxide thereof.
[060] [060] A group of compounds according to this modality are compounds of the formula (I-3a) which are compounds of the formula (I-3) where X is O.
[061] [061] Another group of compounds according to this modality are compounds of the formula (I-3b) which are compounds of the formula (I-3) where X is S.
[062] [062] Another group of compounds according to this modality are compounds of the formula (I-3c) which are compounds of the formula (I-3) in which X is NCH3.
[063] [063] An additional preferred group of compounds according to the invention are those of formula (I-4) which are compounds of formula (I) in which R1 is ethyl or isopropyl and R2 is methyl; R3 is methyl; R4 and R5 are both hydrogen; X is O or S; n is 0 or 1 (preferably, n is 1); or a salt, stereoisomer or N-oxide thereof.
[064] [064] A group of compounds according to this modality are compounds of the formula (I-4a) which are compounds of the formula (I-4) where X is O.
[065] [065] Another group of compounds according to this modality are compounds of the formula (I-4b) which are compounds of the formula (I-4) where X is S.
[066] [066] Certain preferred compounds of formula (I) are: N-ethyl-N '- [5-hydroxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N- methylformamidine; N '- [5-hydroxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-isopropyl-N-methyl-formamidine; N '- [2-chloro-5-hydroxy-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-ethyl-N-methyl-formamidine;
[067] [067] The compounds according to the invention can have any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile, improved physico-chemical properties or increased biodegradability).
[068] [068] Specific examples of compounds of formula (I) are illustrated in Tables 1 to 4 below.
[069] [069] Each of Tables 1 to 4, following Table P below, makes available 48 compounds of the formula (IA) n (IA) in which R2, R3, X and n are as defined in Table P (below ) and R4 and R5 are as defined in Tables 1 to 4, respectively.
[070] [070] Thus, Table 1 identifies 48 compounds of the formula (I-A) in which, for each row in Table P, R4 and R5 are as defined in Table 1; similarly, Table 2 identifies 48 compounds of the formula (I-A) in which, for each row in Table P, R4 and R5 are as defined in Table 2; and so on for Tables 3 and 4. Table P Entry R2 R3 X n P.01 Me HO 0 P.02 Me HO 1 P.03 Me HS 0 P.04 Me HS 1 P.05 Me Cl O 0 P .06 Me Cl O 1 P.07 Me Cl S 0 P.08 Me Cl S 1
[071] [071] Table 1: This table discloses the 48 compounds 1.01 to 1.48 of formula IA in which R4 and R5 are both hydrogen, and in variables R2, R3, X and n have the specific meaning given in the corresponding line in Table P. For example, compound 1.01 has the following structure:
[072] [072] Table 2: This table discloses the 48 compounds 2.01 to 2.48 of formula IA in which R4 and R5 are both methyl, and in variables R2, R3, X and n have the specific meaning given in the corresponding line in Table P.
[073] [073] Table 3: This table discloses the 48 compounds 3.01 to 3.48 of formula IA in which R4 and R5 are both ethyl, and in variables R2, R3, X and n have the specific meaning given in the corresponding line in Table P.
[074] [074] Table 4: This table discloses the 48 compounds 4.01 to 4.48 of formula IA in which R4 and R5 together form a carbonyl group, and in the variables R2, R3, X and n have the specific meaning given in the corresponding line of the Table P.
[075] [075] The compounds of the present invention can be prepared as shown in the following schemes, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I).
[076] [076] The compounds of formula (I), in which R1, R2, R3, R4, R5, X and n are as defined for formula (I), can be obtained by transforming a compound of formula (II) into whereas R3, R4, R5, X and n are as defined for formula (I), by several known methods among which the most widely used are the following: a) Treatment with a compound of formula (III-a), in which R1 and R2 are as defined for formula (I) and R6 is C1-C4 alkyl, in an organic solvent such as toluene or methanol at temperatures between 0 ° C and 100 ° C. b) Treatment with an orthoester of formula (III-b) where R6 is C1-C4 alkyl, followed by treatment with an amine of formula (III-c), in R1 and R2 are as defined for formula (I), in an organic solvent such as methanol at temperatures between 20 ° C and 100 ° C. c) Treatment with a formamide of formula (III-d), where R1 and R2 are as defined for formula (I), and an activating agent such as POCl3 in an inert solvent such as dichloromethane at temperatures between -20 ° C and 40 ° C.
[077] [077] This is shown in Scheme 1 below. Layout 1
[078] [078] The compounds of formula (II), where R3, X and n are as defined for formula (I) and R4 and R5 are hydrogen, can be obtained by transforming a compound of formula (IV), in which R3 , X and n are as defined for formula (I), under reducing conditions, eg by catalytic hydrogenation. This is shown in Scheme 2 below. Layout 2
[079] [079] The compounds of formula (IV), in which R3, X and n are as defined for formula (I), can be obtained by transforming a compound of formula (V), in which R3, X and n are as defined for formula (I), with a transition metal catalyst system under the conditions of olefin metathesis. This is shown in Scheme 3 below. Layout 3
[080] [080] The compounds of formula (V), where R3 and X are as defined for formula (I) and n is 1, can be obtained by transforming a compound of formula (VI), where R3 and X are as defined for formula (I), with a compound of formula (VII), in which R7 is halogen, preferably chlorine or bromine and with a base. This is shown in Scheme 4 below. Scheme 4 base n (V) (VI) (VII)
[081] [081] Alternatively, compounds of formula (I), where R1, R2, R3, X and n are as defined for formula (I) and R4 and R5 are hydrogen, can be obtained by transforming a compound of formula ( VIII), where R1, R2, R3, X and n are as defined for formula (I), under reducing conditions, e.g., by catalytic hydrogenation. This is shown in Scheme 5 below. Layout 5
[082] [082] The compounds of formula (VIII), in which R1, R2, R3, X and n are as defined for formula (I), can be obtained by transforming a compound of formula (IX), in which R1, R2 , R3, X and n are as defined for formula (I), with a transition metal catalyst system under the conditions of olefin metathesis. This is shown in Scheme 6 below. Layout 6
[083] [083] The compounds of formula (IX), in which R1, R2, R3 and X are as defined for formula (I) and n is 1, can be obtained by transforming a compound of formula (IX), in which R1 , R2, R3 and X are as defined for formula (I), with a compound of formula (VII), in which R7 is halogen, preferably chlorine or bromine and with a base. This is shown in Scheme 7 below. Scheme 7 base (X) (VII) n (IX)
[084] [084] The compounds of formula (X), where R1, R2, R3 and X are as defined for formula (I), can be obtained by transforming a compound of formula (XI), in which R1, R2, R3 and X are as defined for formula (I), with a compound of formula (XII), where R8 is MgBr or Li. This is shown in Scheme 8 below. Scheme 8 (XI) (XII) (X)
[085] [085] The compounds of the formula (XI), where R1, R2 and R3 are as defined for the formula (I) and X is O, can be obtained by transforming a compound of the formula (XIII), where R1, R2 and R3 are as defined for formula (I) and R7 is halogen, preferably bromine or iodine, with a compound of the formula (XIV) and with a strong base, such as butyl lithium. This is shown in Scheme 9 below. Scheme 9 (XIII) BuLi (XI) (XIV)
[086] [086] The compounds of the formula (XII), where R1, R2 and R3 are as defined for the formula (I) and R7 is halogen, preferably bromine or iodine, can be obtained by transforming a compound of the formula (XV) , where R3 is as defined for formula (I) and R7 is halogen, preferably bromine or iodine, by several known methods, among which the most widely used are the following: a) Treatment with a compound of the formula (III-a ), where R1 and R2 are as defined for formula (I) and R6 is C1-C4 alkyl, in an organic solvent such as toluene or methanol at temperatures between 0 ° C and 100 ° C. b) Treatment with an orthoester of formula (III-b) where R6 is C1-C4 alkyl, followed by treatment with an amine of formula (III-c), in R1 and R2 are as defined for formula (I), in an organic solvent such as methanol at temperatures between 20 ° C and 100 ° C. c) Treatment with a formamide of formula (III-d), where R1 and R2 are as defined for formula (I), and an activating agent such as POCl3 in an inert solvent such as dichloromethane at temperatures between -20 ° C and 40 ° C.
[087] [087] This is shown in Scheme 10 below. Layout 10
[088] [088] The compounds of formula (XV), where R3 is as defined for formula (I) and R7 is halogen,
[089] [089] Compounds of formula (XVI), where R3 is as defined for formula (I), can be obtained by transforming a compound of formula (XVII), where R3 is as defined for formula (I) , under reducing conditions, eg, by catalytic hydrogenation or under conditions of the Bechamp reaction. This is shown in Scheme 12 below. Layout 12
[090] [090] The compounds of formula (XVII), where R3 is as defined for formula (I), can be obtained by transforming a compound of formula (XVIII), where R3 is as defined for formula (I) , with methyl bromide or methyl iodide and with a base such as sodium hydride or potassium carbonate. This is shown in Scheme 13 below. Layout 13
[091] [091] Certain intermediates described in the above schemes are new and as such form an additional aspect of the invention.
[092] [092] The compounds of formula (I) can be used in the agricultural sector and related areas of use, eg as active ingredients for pest control of plants or in non-living materials for the control of microorganisms that cause deterioration or organisms potentially harmful to man. The new compounds are distinguished by excellent activity at low application rates, by being well tolerated by plants and by being environmentally safe. They have very useful healing, preventive and systemic properties and can be used to protect numerous cultivated plants. The compounds of formula (I) can be used to inhibit or destroy the pests that occur in plants or parts of plants (fruit, flowers, leaves, stems, tubers, roots) from different crops of useful plants, while at the same time also protecting those parts of plants that grow later, eg from phytopathogenic microorganisms.
[093] [093] It is also possible to use compounds of formula (I) as a fungicide. The term "fungicide" as used here means a compound that controls, modifies or prevents the growth of fungi. The term "fungicidal effective amount" means the amount of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Control or modification effects include any deviation from natural development, such as death, retardation and the like, and prevention includes a barrier or other defensive formation on or over a plant to prevent fungal infection.
[094] [094] It is also possible to use compounds of the formula (I) as covering agents for the treatment of plant propagating material, eg, seed, such as fruit, tubers or grains, or plant cuttings (for example rice ), for protection against fungal infections as well as against phytopathogenic fungi occurring in the soil. The propagation material can be treated with a composition comprising a compound of the formula (I) before planting: the seed, for example, can be covered before being sown. The compounds of formula (I) can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing. The invention also relates to such methods of treating plant propagating material and to the plant propagating material so treated.
[095] [095] Furthermore, the compounds according to the present invention can be used for fungi control in related areas, for example in the protection of technical materials, including wood and technical products related to wood, in food storage, in hygiene management.
[096] [096] Additionally, the invention could be used to protect non-living materials from fungal attack, eg, construction wood, wall panels and paint.
[097] [097] The compounds of formula (I) and fungicidal compositions containing them can be used to control plant diseases caused by a broad spectrum of fungal plant pathogens. They are effective in controlling a wide spectrum of plant diseases, such as leaf pathogens from ornamental crops, grass, vegetables, fields, cereals and fruits.
[098] [098] These fungi and disease-causing fungal vectors, as well as phytopathogenic bacteria and viruses, which can be controlled are for example:
[099] [099] Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. including B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp, Claviceps purpurea, Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C. musae, Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechslera spp, Elsinoe spp, Epidermophyton spp, Erwinia amylovora, Erysiphe spp. including E. cichoracearum,
[100] [100] In particular, the compounds of formula (I) and fungicidal compositions containing them can be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the classes of Basidiomycetes, Ascomycetes, Oomycetes and / or Deuteromycetes, Blasocladiomycetes, Critidiomycetes, Glomeromycetes and / or Mucoromycetes.
[101] [101] These pathogens can include: Oomycetes, including diseases caused by Phytophthora, such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthoraoyae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophorathoraphorathoraphorathoraphorathoraphorathoraphorathoraphorathoraphorathoraphorathoraphorathoraphorathoraphorathoraphorathoraphorathoraphorathora diseases caused by Pythium such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; diseases caused by Peronosporales, such as Peronospora destructor,
[102] [102] Ascomycetes, including blotch diseases, blemishes, explosions or pests and / or rot, for example those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Pho herpotrichoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, creberrima Hendersonia, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici- repentis, Alternaria alternata, Alternaria brassicicola, Alternaria solani and Alternaria tomatophila, Capnodiales such as Septoria tritici, Septoria nodorum, Septoria glycines, Cercospora arachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercosporella capsellae and Cercosporella capsellae and Cercosporella capsellae and Cercosporella capsellae richoides, Cladosporium carpophilum, Cladosporium effusum, Passalora fulva, Cladosporium oxysporum, Dothistroma septosporum, Isariopsis clavispora, Mycosphaerella fijiensis, Mycosphaerella graminicola, Mycovellosiella koepkeii, Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporella herpotrichoides, Ramularia beticola, Ramularia collo-cygni, such as Magnaporthales
[103] [103] Basidiomycetes, including soot, for example those caused by Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, ferrugens, for example those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaiae, chrysomyxa arctostaphyleae; Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. Secalis, Pucciniastrum coryli, such as Uredinaliana, Gymnasium, Uredinaliana medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rotting and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisis fucorea, Circumisaria, , Entyloma dahliae, Entylomella microspora, Neovossia moliniae and Tilletia caries.
[104] [104] Blastocladiomycetes, such as Physoderma maydis. Mucoromycetes, such as Choanephora cucurbitarum .; Mucor spp .; Rhizopus arrhizus, as well as diseases caused by other species and genera closely related to those listed above. In addition to their fungicidal activity, compounds and compositions comprising them may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris,
[105] [105] Within the scope of the present invention, target crops and / or useful plants to be protected typically comprise perennial and annual crops, such as berries, for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals, for example barley, maize (maize), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, for example cotton, flax, hemp, jute and sisal; field crops, for example sugar beet and fodder, coffee, hops, mustard, rapeseed (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees, for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses, for example Bermuda grass, blue grass, agrostis, centipede grass, fescue, ryegrass, Saint Augustine grass and Zoysia grass; aromatic herbs such as basil, borage, chives, coriander, lavender, levistico, mint, oregano, parsley, rosemary, sage and thyme; legumes, for example beans, lentils, peas and soy; hard-shelled fruits, for example almond, cashew, peanut seed, hazelnut, peanut, pecan, pistachio and walnut; palms, for example palm oil; ornamental plants, for example flowers, shrubs and trees; other trees, for example cocoa, coconut, olive and rubber; vegetables and greens, for example asparagus, eggplant, broccoli, cabbage, carrot, cucumber, garlic, lettuce, pumpkin, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines, for example grapes.
[106] [106] Useful plants and / or target crops according to the invention include conventional as well as genetically enhanced or manipulated varieties such as, for example, insect resistant varieties (eg, Bt. And VIP varieties) as well as resistant disease-tolerant, herbicide-tolerant (eg, glyphosate and glufosinate-resistant maize varieties commercially available under the trademarks RoundupReady® and LibertyLink®) and nematode-tolerant. By way of example, suitable genetically enhanced or engineered crop varieties include the varieties of Stoneville cotton 5599BR and Stoneville cotton 4892BR.
[107] [107] The term "useful plants" and / or "target crops" is to be understood to also include useful plants that have been made tolerant to herbicides such as bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, inhibitors of ALS, for example primisulfurone, prosulfurone and trifloxysulfurone, EPSPS (5-enol-pyrovyl-chiquimate-3-phosphate synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors as a result of methods conventional breeding or genetic manipulation. An example of a crop that has been made tolerant to imidazolinones, eg imazamox, by conventional breeding methods (mutagenesis) is the Clearfield® summer rapeseed (Canola). Examples of crops that have been made tolerant to herbicides or classes of herbicides by genetic manipulation methods include commercially available varieties of glyphosate and glufosinate resistant under the registered names RoundupReady®, Herculex I® and LibertyLink®.
[108] [108] The term "useful plants" and / or "target crops" is to be understood as including those that naturally are or have been made resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be able to synthesize one or more toxins with selective action, as they are known, for example, from toxin-producing bacteria. Examples of toxins that can be expressed include δ-endotoxins, vegetative insecticidal proteins (Vip), nematode-colonizing bacteria insecticidal proteins and toxins produced by scorpions, arachnids, wasps and fungi. An example of a culture that has been modified to express Bacillus thuringiensis toxin is Bt KnockOut (Syngenta Seeds). An example of a culture comprising more than one gene that encodes insecticidal resistance and thus expresses more than one toxin is VipCot  (Syngenta Seeds). Crops or their seed material can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification). For example, a plant may have the ability to express an insecticidal protein while at the same time being tolerant to herbicides, for example Herculex I (Dow AgroSciences, Pioneer Hi-Bred International).
[109] [109] The term "useful plants" and / or "target crops" is to be understood as including also useful plants that have been so transformed by the use of recombinant DNA techniques that they are capable of synthesizing antipathogenic substances having a selective action, such as , for example, the so-called “pathogenesis-related proteins” (PRP,
[110] [110] Toxins that can be expressed by transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, eg, Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), eg, Vip1, Vip2 , Vip3 or Vip3A; or insecticidal proteins from nematode-colonizing bacteria, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect specific neurotoxins; toxins produced by fungi, such as Streptomyces toxins, plant lectins, such as pea lectins, barley lectins, or white bell lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome inactivating proteins (RIP), such as ricin, more RIP, abrina, lufina, saporina or briodina; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA reductase, ion channel blockers, such as sodium or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
[111] [111] Additionally, in the context of the present invention, they are to be understood as δ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example, Vip1 , Vip2, Vip3 or Vip3A, also expressly hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of these proteins (see, for example, WO 02/15701). Truncated toxins are known, for example a truncated Cry1Ab. In the case of modified toxins, one or more naturally occurring toxin amino acids are replaced. In such amino acid substitutions, non-naturally present protease recognition sequences are preferably inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin G recognition sequence is inserted into a Cry3A toxin (see WO03 / 018810).
[112] [112] Further examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374 753, WO93 / 07278, WO95 / 34656, EP-A-0 427 529, EP-A -451 878 and WO03 / 052073.
[113] [113] The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
[114] [114] The toxin contained in transgenic plants gives plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially and commonly found in beetles (Coleoptera), double-winged insects (Diptera) and butterflies (Lepidoptera).
[115] [115] Transgenic plants containing one or more genes that encode an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard (variety of maize that expresses a Cry1Ab toxin); YieldGard Rootworm (variety of maize that expresses a Cry3Bb1 toxin); YieldGard Plus (variety of maize that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink (variety of maize that expresses a Cry9C toxin); Herculex I (variety of maize that expresses a Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B (cotton variety that expresses a Cry1Ac toxin); Bollgard I (cotton variety that expresses a Cry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac toxin and a Cry2Ab toxin); VipCot (cotton variety that expresses a Vip3A toxin and a Cry1Ab); NewLeaf (potato variety that expresses a Cry3A toxin); NatureGard, Agrisure® GT Advantage (glyphosate tolerant trait GA21), Agrisure® CB Advantage (corn borer tolerant trait (CB) Bt11) and Protecta.
[116] [116] Additional examples of such transgenic crops are:
[117] [117] The term “locus” as used here means fields in or on which plants are growing or where seeds of cultivated plants are sown or where the seeds will be placed in the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
[118] [118] The term "plants" refers to all the physical parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, stems, foliage and fruits.
[119] [119] It is understood that the term "plant propagating material" denotes generative parts of the plant, such as seeds, that can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants can be mentioned. Germinated plants and young plants to be transplanted after germination or after emergence from the soil can also be mentioned. These young plants can be protected before transplantation by total or partial immersion treatment. Preferably, "plant propagation material" is understood to denote seeds.
[120] [120] Pesticide agents referred to here using their common name are known, for example, from “The Pesticide Manual”, 15th Ed., British Crop Protection Council
[121] [121] The compounds of formula (I) can be used in unmodified form or, preferably, in conjunction with adjuvants conventionally employed in the formulation technique. For this purpose, emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dust, granules and also encapsulations, e.g., in polymeric substances can be conveniently formulated in a known manner. As with the type of compositions, the application methods, such as spraying, atomizing, dusty, dispersing, coating or spilling, are chosen according to the intended objectives and the prevailing circumstances.
[122] [122] Suitable carriers and adjuvants, eg for agricultural use, can be solid or liquid and are useful substances in formulation technology, eg natural or regenerated mineral substances, solvents, dispersants, wetting agents, stickiness promoters , thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
[123] [123] Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-sedimentation agents and dispersing agents and may additionally include a wetting agent to enhance the activity as well as a defoamer and a crystal growth inhibitor. In use, these concentrates are diluted with water and usually applied as a spray to the area to be treated. The amount of active ingredient can vary from 0.5% to 95% of the concentrate.
[124] [124] Wettable powders are in the form of finely divided particles that disperse rapidly in water or other liquid vehicles. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include Fuller earth, kaolin clays, silica and other readily moist organic or inorganic solids. Wettable powders normally contain 5%
[125] [125] Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and others non-volatile organic solvents. In use, these concentrates are dispersed in water or another liquid and usually applied as a spray to the area to be treated. The amount of active ingredient can vary from 0.5% to 95% of the concentrate.
[126] [126] Granular formulations include both extruded and relatively coarse particles and are usually applied without dilution to the area where treatment is required. Typical carriers for granular formulations include sand, Fuller earth, atapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, crushed corn cobs, crushed peanut shells, sugars, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate and other organic or inorganic materials that absorb or can be coated with the active compound. Granular formulations normally contain 5% to 25% of active ingredients that may include surfactants such as heavy aromatic naphthas, kerosene and other fractions of petroleum or vegetable oils; and / or adherents such as dextrins, glue or synthetic resins.
[127] [127] Dusts are free-flowing mixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids that act as dispersants and carriers.
[128] [128] Microcapsules are typically droplets or granules of the active ingredient encased in an inert porous shell that allows the enclosed material to escape into the vicinity at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter. The enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and can include a solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form within the granule pores. The granules typically range from 1 millimeter to 1 centimeter and preferably 1 to 2 millimeters in diameter. The granules are formed by extrusion, agglomeration or pelletizing or occur naturally. Examples of such materials are vermiculite, sintered clay, kaolin, atapulgite clay, sawdust and granular coal. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthate.
[129] [129] Other formulations useful for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprayers can also be used, in which the active ingredient is dispersed in a finely divided form due to the vaporization of a dispersing solvent vehicle with a low boiling point.
[130] [130] Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the types of formulations described above are well known to those skilled in the art.
[131] [131] Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone , chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, ether diethylene glycol methyl, N, N-dimethylformamide, dimethylsulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidinone, ethyl acetate, 2-ethyl-hexanol, 1-ethylene hexanol , 1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, triacetatat glycerol, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone,
[132] [132] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, atapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller earth, shells cotton seeds, wheat flour, soy flour, pumice stone, wood flour, nutshell flour and lignin.
[133] [133] A wide range of surfactants is advantageously employed in said liquid and solid compositions, especially those designed to be diluted with a vehicle before application. These agents, when used, normally comprise from 0.1% to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be used as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surfactants include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as C 18 nonylphenol-ethoxylate; alcohol-alkylene oxide addition products, such as C 16 tridecyl ethoxylate alcohol; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di (2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.
[134] [134] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming agents, light blocking agents, compatibilizing agents, antifoaming agents , sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, flavorings, spreading agents, penetration aids, micronutrients, emollients, lubricants and adhesives.
[135] [135] In addition, in addition, other biocidal active ingredients or compositions can be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these additional active ingredients can be formulated together with the compositions of the invention or mixed, for example, in the spray tank. These biocidal active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and / or plant growth regulators.
[136] [136] In addition, the compositions of the invention can also be applied with one or more inductors of systemically acquired resistance ("SAR" inductor). SAR inducers are known and described, for example, in United States Patent No. 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
[137] [137] The compounds of formula (I) are normally used in the form of compositions and can be applied to the area of the crop or plant to be treated, simultaneously or in succession with additional compounds. These additional compounds can be, for example, fertilizers or micronutrient donors or other preparations, which influence plant growth. They can also be selective herbicides or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired in conjunction with additional carriers, surfactants or application-promoting adjuvants commonly employed in the formulation technique.
[138] [138] The compounds of the formula (I) can be used in the form of compositions (fungicides) to control or protect against phytopathogenic microorganisms, comprising as active ingredient at least one compound of the formula (I) or at least one preferred individual compound as defined above, in the free form or in the form of agrochemically usable salt, and at least one of the adjuvants mentioned above.
[139] [139] The invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound of the formula (I), an agriculturally acceptable carrier and optionally an adjuvant. An acceptable agricultural carrier is, for example, a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, said composition may comprise at least one or more pesticide-active compounds, for example a fungicidal active ingredient in addition to the compound of formula (I).
[140] [140] The compound of formula (I) can be the only active ingredient in a composition or it can be mixed with addition with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient can, in some cases, result in unexpected synergistic activities.
[141] [141] Examples of suitable additional active ingredients include the following: 1,2,4-thiadiazoles, 2,6-
[142] [142] An additional aspect of the invention relates to a method of controlling or preventing plant infestation, eg, useful plants such as crop plants, their propagating material, eg, seeds, crops collected , eg cultures collected from food or non-living materials by phytopathogenic microorganisms or that cause deterioration or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula (I) or an individual compound preferential as defined above as an active ingredient for plants, parts of plants or their locus, propagating material or any part of non-living materials.
[143] [143] Control or prevention means reducing infestation by insects or phytopathogenic microorganisms or causing deterioration or organisms potentially harmful to man, especially fungal organisms, to a level where an improvement is demonstrated.
[144] [144] A preferred method of controlling or preventing the infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects that comprise the application of a compound of formula (I), or an agrochemical composition that contains at least one of these compounds, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen or insect. However, the compounds of the formula (I) can also penetrate the plant through the roots through the soil (systemic action), by soaking the plant's locus with a liquid formulation or by applying the compounds in solid form to the soil, e.g. , in granular form (application to the soil). In irrigated rice crops, such granules can be applied to the irrigated rice field. The compounds of formula (I) can also be applied to seeds (coating) by impregnating the seeds or tubers with a liquid formulation of the fungicide or by coating them with a solid formulation.
[145] [145] A formulation, e.g. a composition containing the compound of formula (I) and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula (I) can be prepared in a known manner, typically by intimate mixing and / or grinding the compound with diluents, for example solvents, solid carriers and, optionally, surfactant compounds.
[146] [146] Application methods for compositions, that is, pest control methods of the aforementioned type, such as spraying, atomizing, dusty, brushing, covering, dispersing or spilling - which are to be selected to suit intended objectives of the prevailing circumstances - and the use of pest control compositions of the type mentioned above are other matters of the invention. Typical concentration rates are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The application rate per hectare is preferably 1 g to 2000 g of active ingredient per hectare, more preferably 10 to 1000 g / ha, most preferably 10 to 600 g / ha. When used as a seed drenching agent, convenient dosages are 10 mg to 1 g of active substance per kg of seeds.
[147] [147] When the combinations of the present invention are used for seed treatment, rates of 0.001 to 50 g of a compound of formula (I) per kg of seeds, preferably from 0.01 to 10 g per kg of seeds, are generally enough.
[148] [148] Suitably, a composition comprising a compound of formula (I) according to the present invention is applied preventively, meaning before the development of the disease, or curatively, meaning after the development of the disease.
[149] [149] The compositions of the invention can be used in any conventional form, for example in the form of a double pack, a dry seed treatment powder (DS), a seed treatment emulsion (ES), a concentrate suitable for flow for seed treatment (FS), a seed treatment solution (LS), a water-dispersible powder for seed treatment (WS), a suspension of seed treatment capsules (CF), a seed treatment gel (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspoemulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a microemulsion (ME), an oil dispersion (OD), an oil miscible fluid (OF), an oil miscible liquid (OL ), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
[150] [150] Such compositions can be produced in a conventional manner, eg by mixing the active ingredients with appropriate formulation aggregates (diluents, solvents, fillers and optionally other formulation ingredients such as surfactants, biocides, antifreeze,
[151] [151] A seed cover formulation is applied in a manner known per se to seeds using the combination of the invention and a diluent in the form of a suitable seed cover formulation, eg as an aqueous suspension or in a form of dry powder with good adhesion to the seeds. Such seed cover formulations are known in the art. Seed cover formulations can contain the single active ingredients or the combination of active ingredients in an encapsulated form, eg as slow release capsules or microcapsules.
[152] [152] In general, formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% of agriculturally acceptable surfactant and 10 to 99.99% of solid or liquid formulation aggregates and adjuvant (s) , the active agent consisting of at least the compound of formula (I) together with components (B) and (C) and, optionally, other active agents, particularly microbiocides or preservatives or the like. Concentrated forms of compositions generally contain between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Forms of application of the formulation may contain, for example, 0.01 to 20% by weight, preferably 0.01 to 5% by weight of active agent. While commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
[153] [153] While it is preferable to formulate commercial products as concentrates, the end user will normally use diluted formulations. EXAMPLES
[154] [154] The following Examples serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater effectiveness at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates, if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.
[155] [155] Throughout this description, temperatures are given in degrees Celsius and "p.f." means melting point. LC / MS stands for Liquid Chromatography Mass Speculation Formulation Examples Wettable Powders a) b) c) active ingredient [25% 50% 75% formula (I) compound]
[156] [156] The active ingredient is carefully mixed with the adjuvants and the mixture is carefully ground in a suitable mill, giving rise to wettable powders that can be diluted with water to give suspensions of the desired concentration.
[157] [157] The active ingredient is carefully mixed with the adjuvants and the mixture is carefully ground in a suitable mill, giving rise to powders that can be used directly for seed treatment.
[158] [158] Emulsions of any required dilution, which can be used to protect plants, can be obtained from this concentrate by dilution with water.
[159] [159] Ready-to-use dust is obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry seed coating.
[160] [160] The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a draft.
[161] [161] The finely ground active ingredient is uniformly applied, in a mixer, to kaolin moistened with polyethylene glycol. In this way, coated, non-dusty granules are obtained. Concentrate in suspension active ingredient [compound of the formula (I)] 40% propylene glycol 10% nonylphenol polyethylene glycol ether (15 6 mol% ethylene oxide) Sodium lignosulfonate 10% carboxymethylcellulose 1% silicone oil (in the form of an emulsion to 1% 75% in water) Water 32%
[162] [162] The finely crushed active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by diluting with water. Using such dilutions, live plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, spilling or immersion. Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 40% propylene glycol 5% butanol PO / EO copolymer 2% tristyrenophenol with 10-20 moles of 2% EO 1,2-benzisothiazolin-3-one (in the form of a 0.5% 20% solution in water) 5% monoazo pigment calcium salt Silicone oil (in the form of a 0.2% emulsion 75% in water) 45.3% water
[163] [163] The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by diluting with water. Using such dilutions, live plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, spilling or immersion. Suspension of Slow Release Capsules
[164] [164] 28 parts of a combination of the compound of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of a mixture of toluene diisocyanate / polymethylene polyphenylisocyanate (8: 1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is reached. To this emulsion is added a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water. The mixture is stirred until the polymerization reaction is completed.
[165] [165] The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The average diameter of the capsules is 8-15 microns.
[166] [166] The resulting formulation is applied to seeds as an aqueous suspension in a device suitable for that purpose. Preparation examples
[167] [167] Example 1: This example illustrates the preparation of N-ethyl-N '- [5-methoxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-methyl -formamidine (Compound 1.22) Preparation of N-ethyl-N '- [5-methoxy-2-methyl-4- (2,2,2-trifluoroacetyl) phenyl] -N-methyl-formamidine N' - (4-bromo -5-methoxy-2-methyl-phenyl) -N-ethyl-N-methyl-formamidine (6.0 g, 21.04 mmol) was dissolved in tetrahydrofuran (84 mL) and cooled to -78 ° C. A 2 N n-butyl lithium solution in cyclohexane (18.9 mL, 37.87 mmol) was added dropwise. The resulting yellow solution was stirred for 1 h at -78 ° C.2,2,2-Ethyl trifluoroacetate (8.97 g, 63.128 mmol) was added dropwise. At the end of the addition, the cooling bath was removed and the reaction was heated to 0-5 ° C and then quenched with a saturated solution of ammonium chloride. The mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
[168] [168] The residue was purified by chromatography on silica gel, using ethyl acetate / dichloromethane as the eluent system, to give N-ethyl-N '- [5-methoxy-2-methyl- 4- (2,2,2 -trifluoroacetyl) phenyl] -N-methyl-formamidine (5.1 g, 16.89 mmol).
[169] [169] Majority isomer: 1H-NMR (400 MHz, CDCl3): δ = 1.27 (t, 3H), 2.22 (s, 3H), 3.08 (s, 3H), 3.41 (d , 2H), 3.90 (s, 3H), 6.36 (ls, 1H), 7.56 (ls, 2H) Minor isomer: 1H-NMR (400 MHz, CDCl3): δ = 1.27 (t , 3H), 2.22 (s, 3H), 3.08 (s, 3H), 3.62 (d, 2H), 3.90 (s, 3H), 6.36 (s, 1H), 7 , 50 (s, 1H), 7.56 (ls, 1H) E / Z ratio: 3: 5 Preparation of N-ethyl-N '- [4- [1-hydroxy-1- (trifluoromethyl) ally] -5 -methoxy-2-methyl-phenyl] -N-methyl-formamidine A a solution of N-ethyl-N '- [5-methoxy-2-methyl-4- (2,2,2-trifluoroacetyl) phenyl] -N -methyl-formamidine (2.00 g, 6.29 mmol) in tetrahydrofuran (7 mL) was added bromine (vinyl) magnesium (7.23 mL, 7.23 mmol) dropwise at -5 ° C and the reaction mixture was stirred at 0 ° C for 45 min. The reaction mixture was filtered and poured into cooled water (15 ml), then aqueous ammonium chloride solution was added until the precipitate disappeared and the mixture was extracted with ethyl acetate (3 X 20 ml). The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo to give N-ethyl-N '- [4- [1-hydroxy-1- (trifluoromethyl) ally] -5-methoxy-2 -methyl-phenyl] -N-methyl-formamidine (2.20 g, 5.99 mmol). This material was used as crude for the next step.
[170] [170] 1H-NMR (400 MHz, CDCl3): δ = 7.46 (1H, m), 7.07 (1H, s), 6.42 (2H, m), 6.31 (1H, s) , 5.77 (1H, d), 5.52 (1H, d), 3.93 (3H, ls), 3.36 (2H, m), 3.03 (3H, s), 2.21 ( 3H, s), 1.24 (3H, t) Preparation of N '- [4- [1-allyloxy-1- (trifluoromethyl) ally] -5-methoxy-2-methyl-phenyl] -N-ethyl-N -methyl-formamidine A solution of N-ethyl-N '- [4- [1-hydroxy-1- (trifluoromethyl) ally] -5-methoxy-2-methyl-phenyl] -N-methyl-formamidine (2, 25 g, 6.13 mmol) in N, N-dimethylformamide (24.5 mL) sodium hydride (0.258 g, 6.74 mmol) was added portion by portion. The reaction mixture was stirred at room temperature for 30 min. Then, allyl bromide (0.536 ml, 6.13 mmol) was added dropwise and the reaction mixture was stirred at room temperature overnight. The reaction mixture was quenched with slow addition of saturated aqueous ammonium chloride solution (20 ml) and then extracted with ethyl acetate (3 X 15 ml). The combined organic layers were washed with water (2 X 100 ml), brine, dried over sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by chromatography on silica gel using ethyl acetate / cyclohexane as the eluent system, to administer N '- [4- [1-allyloxy-1- (trifluoromethyl) ally] -5-methoxy-2- methyl-phenyl] -N-ethyl-N-methyl-formamidine (1.99 g, 5.3 mmol).
[171] [171] 1H-NMR (400MHz, DMSO): δ = 1.14 (t, 3H), 2.12 (s, 3H), 2.86-3.08 (m, 3H), 3.44 (m , 2H), 3.70 (s, 3H), 3.85 (d, 2H), 5.17 (dd, 1H), 5.33 (m, 2H), 5.49 (d, 1H), 5 , 93 (1H,
[172] [172] The crude material was purified by chromatography on silica gel using ethyl acetate / cyclohexane as the eluent system to administer N-ethyl-N '- [5-methoxy-2-methyl-4- [5- (trifluoromethyl ) -2H-furan-5-yl] phenyl] - N-methyl-formamidine (0.90 g, 2.6 mmol).
[173] [173] 1H-NMR (400MHz, DMSO): δ = 8.22-8.62 (1H, m), 7.49 (1H, s), 7.14 (2H, m), 6.26-6 , 69 (2H, m), 4.59-4.92 (2H, m), 3.86 (3H, s), 3.57-3.78 (2H, m), 3.28-3.36 (3H, m), 2.30 (3H, m), 1.28 (3H, t).
[174] [174] Preparation of N-ethyl-N '- [5-methoxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-methyl-formamidine (Compound 1.22) N-ethyl-N '- [5-methoxy-2-methyl-4- [5- (trifluoromethyl) -2H-furan-5-yl] phenyl] -N-methyl-formamidine solution (200 mg, 0.58 mmol) in ethanol (6 mL) was degassed with argon and palladium on charcoal (0.01869 g, cat.) was added. The reaction mixture was stirred under a hydrogen atmosphere at room temperature for 4 h. The reaction mixture was filtered through celite and the filtrate was concentrated in vacuo. The solid was adsorbed on water (20 ml) and acidified with HCl until pH 1. The mixture was extracted with diethyl ether (10 ml) and the aqueous layer was basified with NaHCO3. The mixture was extracted with dichloromethane (3 X 10 ml) and the combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo to give N-ethyl-N'- [5-methoxy-2-methyl -4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-methyl-formamidine (Compound 1.22, 98 mg, 0.29 mmol).
[175] [175] 1H-NMR (400MHz, DMSO): δ = 7.72 (1H, s), 7.27 (1H, s), 6.48 (1H, s), 3.77 (4H, s), 3.33 (2H, m), 2.99 (3H, sl), 2.64 (1H, ddd), 2.38 (1H, dt), 2.10 (3H, s), 2.00 (2H , m), 1.14 (3H, m). Table E: Physical data (LC / MS) of certain compounds of formula (I) LC / M method (Liquid Chromatography Mass Spectrometry) used: (Waters ACQUITY UPLC, Phenomenex Gemini C18 column, particle size 3 µm, 110 Angström, 30 x 3 mm, 1.7 mL / min, 60 ° C, H2O + 0.05% (95%) HCOOH / 4: 1 CH3CN / MeOH + 0.04% (5%) HCOOH - 2 min - CH3CN / MeOH 4: 1 + 0.04% HCOOH (5%) - 0.8 min, Waters ACQUITY SQD Mass Spectrometer, ionization method: electrospray (ESI), Polarity: positive ions, Capillary (kV ) 3.00, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (° C) 150, Desolvation Temperature (° C) 400, Gas Flow in the Cone (L / Hr) 60 , Desolvation Gas Flow (L / Hr) 700)).
[176] [176] Leaf segments of wheat cv. Kanzler were placed on agar in a multi-well plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf discs were inoculated by agitation by plants infected with powdery mildew over the test plates 1 day after application. The inoculated leaf discs were incubated at 20 ° C and rh at 60% under a 24 h dark light regime followed by 12 h light / 12 h dark in a climate-controlled chamber and the activity of a compound was evaluated as a percentage disease control compared to no treatment when an appropriate level of disease damage appears in untreated leaf control segments (6 - 8 days after application).
[177] [177] The following compounds gave disease control of at least 80% at 200 ppm in this test compared to untreated control leaf discs under the same conditions, which show extensive disease development:
[178] [178] Four-week-old soy plants are sprayed in a spray chamber with the formulated test compound diluted in water. Leaf discs are cut from treated plants and placed on agar in 24-well plates one day after application. The leaf discs are inoculated by spraying them with a spore suspension on their lower leaf surface. After an incubation period in an air-conditioned chamber of 24-36 hours in the dark at 20 ° C and rh at 75%, the leaf discs are then kept at 20 ° C with 12 h of light / day and rh at 75%. The percentage of leaf disc area covered by disease is assessed when an appropriate level of disease appears in untreated control plants (12 - 14 days after application).
[179] [179] The following compounds gave disease control of at least 80% at 200 ppm in this test compared to untreated leaf control discs under the same conditions, which show extensive disease development:
[180] [180] Leaf segments of wheat cv. Kanzler were placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf discs were inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments were incubated at 19 ° C and rh at 75% under a light regime of 12 h of light / 12 h of darkness in an air-conditioned chamber and the activity of a compound was evaluated as a percentage of disease control in comparison with no treatment when an appropriate level of damage caused by the disease appears in untreated leaf control segments (7 - 9 days after application).
[181] [181] The following compounds gave disease control of at least 80% at 200 ppm in this test compared to untreated leaf control discs under the same conditions, which show extensive disease development:
[182] [182] Leaf segments of wheat cv. Kanzler are placed on agar in multi-well plates (24-well format). The leaf segments are inoculated with a spore suspension of the fungus. The plates were stored in the dark at 19 ° C and rh at 75%. The formulated test compound diluted in water was applied 1 day after inoculation. The leaf segments were incubated at 19 ° C and rh at 75% under a light regime of 12 h of light / 12 h of darkness in an air-conditioned chamber and the activity of a compound was evaluated as a percentage of disease control compared to no treatment when an appropriate level of damage from the disease appears in untreated leaf control segments (6 - 8 days after application).
[183] [183] The following compounds gave disease control of at least 80% at 200 ppm in this test compared to untreated leaf control discs under the same conditions, which show extensive disease development:
1.21 and 1.22

权利要求:
Claims (15)
[1]
1. A compound of the formula (I) n (I) in which R1 and R2 are each independently selected from C1-C4 alkyl and C3-C8 cycloalkyl; or R1 and R2 together with the nitrogen atom to which they are attached form a saturated cyclic group with three to six members; R3 is hydrogen, halogen or C1-C4 alkyl; R4 and R5 are each independently selected from hydrogen and C1-C4 alkyl; or R4 and R5 together with the carbon atom to which they are attached form a carbonyl group (C = O); X is O, S or NCH3; n is 0 or 1; or a salt thereof, metal complex, stereoisomer or N-oxide.
[2]
A compound according to claim 1, wherein R1 and R2 are each independently C1-C4 alkyl.
[3]
A compound according to either of claims 1 or 2, wherein R3 is halogen or C1-C3 alkyl.
[4]
A compound according to any one of claims 1, 2 or 3, wherein R4 and R5 are each independently selected from hydrogen and methyl, or R4 and R5 together with the carbon atom to which they are attached form a group carbonyl.
[5]
A compound according to any one of claims 1, 2, 3 or 4, wherein R1 and R2 are each independently selected from methyl, ethyl and isopropyl.
[6]
A compound according to any one of claims 1, 2, 3, 4 or 5, wherein R3 is fluorine, chlorine or methyl.
[7]
A compound according to any one of claims 1, 2, 3, 4, 5 or 6, wherein R4 and R5 are both hydrogen, or R4 and R5 together with the carbon atom to which they are attached form a group carbonyl.
[8]
A compound according to any one of claims 1, 2, 3, 4, 5, 6 or 7, wherein R1 is methyl, ethyl or isopropyl; R2 is methyl or ethyl.
[9]
A compound according to any one of claims 1, 2, 3, 4, 5, 6, 7 or 8, wherein R3 is chlorine or methyl and R4 and R5 are both hydrogen.
[10]
A compound according to claim 1, wherein R1 and R2 are each independently selected from methyl, ethyl and isopropyl; R3 is fluorine, chlorine or methyl; R4 and R5 are both hydrogen, or R4 and R5 together with the carbon atom to which they are attached form a carbonyl group; X is O, S or NCH3; n is 0 or 1;
or a salt thereof, metal complex, stereoisomer or N-oxide.
[11]
A compound according to claim 1, wherein the compound is selected from: N-ethyl-N '- [5-hydroxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl ] phenyl] -N-methyl-formamidine; N '- [5-hydroxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-isopropyl-N-methyl-formamidine; N '- [2-chloro-5-hydroxy-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-ethyl-N-methyl-formamidine;
N-ethyl-N '- [5-hydroxy-2-methyl-4- [4-oxo-2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-methyl-formamidine; N-ethyl-N '- [5-hydroxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrothiophen-2-yl] phenyl] -N-methyl-formamidine; or N-ethyl-N '- [5-hydroxy-2-methyl-4- [2- (trifluoromethyl) oxetan-2-yl] phenyl] -N-methyl-formamidine; or a salt thereof, metal complex, stereoisomer or N-oxide.
[12]
A compound according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, wherein X is O or S.
[13]
A composition comprising a fungicidal effective amount of a compound of formula (I), as defined in any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
[14]
Composition according to claim 13, wherein the composition additionally comprises at least one additional active ingredient and / or a diluent.
[15]
15. A method of combating, preventing or controlling phytopathogenic fungi that includes application to phytopathogenic fungi to the locus of phytopathogenic fungi or to a plant susceptible to attack by phytopathogenic fungi, or to their propagation material, in an fungicidal effective amount of a compound of the formula (I), as defined in any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, or a composition comprising a fungicidal effective amount of a compound of the formula (I), as defined in any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

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WO2021244952A1|2020-06-03|2021-12-09|Syngenta Crop Protection Ag|Microbiocidal derivatives|

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WO2021244950A1|2020-06-03|2021-12-09|Syngenta Crop Protection Ag|Fungicidal compositions|

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WO2022013417A1|2020-07-17|2022-01-20|Syngenta Crop Protection Ag|Pesticidally active heterocyclic derivatives with sulfur containing substituents|

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WO2022043576A2|2020-08-31|2022-03-03|Syngenta Crop Protection Ag|Pesticidally active heterocyclic derivatives with sulfur containing substituents|

法律状态:
2021-12-07| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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EP17205304.3|2017-12-04|

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EP17205304|2017-12-04|

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PCT/EP2018/083052|WO2019110427A1|2017-12-04|2018-11-29|Microbiocidal phenylamidine derivatives|

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